EP3405515B1 - Utilisation du z-hfo-1,1,1,4,4,4-hexafluoro-2-butène dans des applications d'expansion à haute température - Google Patents

Utilisation du z-hfo-1,1,1,4,4,4-hexafluoro-2-butène dans des applications d'expansion à haute température Download PDF

Info

Publication number
EP3405515B1
EP3405515B1 EP17702249.8A EP17702249A EP3405515B1 EP 3405515 B1 EP3405515 B1 EP 3405515B1 EP 17702249 A EP17702249 A EP 17702249A EP 3405515 B1 EP3405515 B1 EP 3405515B1
Authority
EP
European Patent Office
Prior art keywords
foaming
polyisocyanate
active hydrogen
composition
hexafluoro
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17702249.8A
Other languages
German (de)
English (en)
Other versions
EP3405515A1 (fr
Inventor
Ernest Byron Wysong
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chemours Co FC LLC
Original Assignee
Chemours Co FC LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chemours Co FC LLC filed Critical Chemours Co FC LLC
Publication of EP3405515A1 publication Critical patent/EP3405515A1/fr
Application granted granted Critical
Publication of EP3405515B1 publication Critical patent/EP3405515B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143Halogen containing compounds
    • C08J9/144Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/02Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by the reacting monomers or modifying agents during the preparation or modification of macromolecules
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/14Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1833Catalysts containing secondary or tertiary amines or salts thereof having ether, acetal, or orthoester groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0025Foam properties rigid
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00Foams characterised by the foaming process
    • C08J2201/02Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00Foams characterized by the expanding agent
    • C08J2203/16Unsaturated hydrocarbons
    • C08J2203/162Halogenated unsaturated hydrocarbons, e.g. H2C=CF2
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/04Foams characterised by their properties characterised by the foam pores
    • C08J2205/052Closed cells, i.e. more than 50% of the pores are closed
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00Foams characterised by their properties
    • C08J2205/10Rigid foams
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00Foams characterised by their intended use
    • C08J2207/04Aerosol, e.g. polyurethane foam spray
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04Polyurethanes
    • C08J2375/08Polyurethanes from polyethers

Definitions

  • This invention relates to the foaming of the reaction product of polyisocyanate and active hydrogen-containing compound such as polyol in the presence of Z-HFO-1,1,1,4,4,4-hexafluoro-2-butene blowing agent at high temperature.
  • EP 2 447 310 discloses the use of 1336mzzm as being 1,1,1,3,3,3-hexafluorobutene and being applicable as a blowing agent to produce polyurethane and polyisocyanurate foams, but having the disadvantage of the foams having high thermal conductivity arising from the above atmospheric pressure boiling point of this compound [0007-0008].
  • the correct identity of 1336mzzm which is the same as 1336mzz, is 1,1,1,4,4,4-hexafluoro-2-butene.
  • the Z- isomer has a boiling point of 33°C.
  • EP'310 overcomes this problem by combining the 1336mzz with 1-chloro-3,3,3-trifluoropropene (1233zd) as the blowing agent to produce the polyurethane and polyisocyanurate foams.
  • the maximum temperature of the raw materials used in the foaming process which is the foaming temperature is disclosed to be 70°F (21.1°C) [0051].
  • the raw materials are the polyol masterbatch and the polyisocyanate, which are commonly referred to as the B-side and A-side compositions (reactants), respectively.
  • JP H05 179043 A describes a blowing agent comprising cis-1,1,1,4,4,4-hexafluoro-2-butene.
  • the blowing agent can be mixed with silicone foam stabilizer, water, N,N,N',N'-tetramethylhexane-1,6-diamine and further be blended with polymethylene polyphenyl isocyanate to obtain a rigid polyurethane foam.
  • the present invention is the process comprising reacting polyisocyanate with active hydrogen-containing compound being polyol in the presence of Z-1,1,1,4,4,4-hexafluoro-2-butene (Z-1336mzz) at a temperature of at least 135°F (57.2 °C) to obtain as a result thereof, foamed reaction product.
  • Z-1336mzz is the blowing agent causing the reaction product to foam.
  • the reaction temperature is also the foaming temperature.
  • the foaming temperature is the temperature of the polyisocyanate and active hydrogen-containing reactants and the compositions containing these reactants i.e. the A-side composition containing the polyisocyanate and the B-side composition containing the active-hydrogen-containing compound. This is the temperature of the reactants and their respective compositions (A-side and B-side) at the time of feeding to the apparatus that mixes them together, resulting in production of the foamed reaction product.
  • the maximum foaming temperature is application dependent in the sense that increasing foaming temperature is accompanied by increasing reaction rate.
  • the foaming temperature should not be so high that it is detrimental to the foamed reaction product. The most common detriment would be an increase in thermal conductivity.
  • the preferred maximum foaming temperature is 150°F (65.6°C).
  • the present invention contemplates foaming temperatures of 135°F(57.2°C) to 150°F(65.6°C), 135°F(57.2°C) to 145°F(62.8°C), and 140°F(60.0°C) to 145°F(62.8°C) and 140°F(60.0°C) to 150°F(65.6°C).
  • the reaction product that is foamed is preferably polyurethane or polyisocyanurate or a mixture of these polymers.
  • the active hydrogen-containing compound reactant in the process of the present invention includes those described in U.S. Patent No. 4,394,491 and in WO 2014/- 113379 (isocyanate-reactive groups).
  • Active hydrogen means that the hydrogen of the active-hydrogen-containing polyol compound is reactive with the isocyanate of the polyisocyanate reactant.
  • the active hydrogen-containing polyol compound contains at least two groups that contain active hydrogen (atoms). Some of the hydroxyl groups can be replaced by amine groups, whereby the active hydrogen-containing compound contains both hydroxyl and amine groups.
  • the compound contains at least two hydroxyl groups, whereby the compound is a polyol. Examples of such polyols are those which have an equivalent weight of about 50 to about 700, normally of about 70 to about 300, more typically of about 90 to about 270, and carry at least 2 hydroxyl groups, usually 3 to 8 such groups.
  • polyester polyols such as aromatic polyester polyols, e.g., those made by transesterifying polyethylene terephthalate (PET) scrap with a glycol such as diethylene glycol, or made by reacting phthalic anhydride with a glycol.
  • PET polyethylene terephthalate
  • the resulting polyester polyols may be reacted further with ethylene and/or propylene oxide to form an extended polyester polyol containing additional internal alkyleneoxy groups.
  • suitable polyols also comprise polyether polyols such as polyethylene oxides, polypropylene oxides, mixed polyethylene-propylene oxides with terminal hydroxyl groups, among others.
  • suitable polyols can be prepared by reacting ethylene and/or propylene oxide with an initiator having 2 to 16, generally 3 to 8 hydroxyl groups as present, for example, in glycerol, pentaerythritol and carbohydrates such as sorbitol, glucose, sucrose and the like polyhydroxy compounds.
  • Suitable polyether polyols can also include aliphatic or aromatic amine-based polyols.
  • polyol also containing amine is the Mannich polyol.
  • polyisocyanate component (reactant) it is normally selected in such proportion relative to that of the active hydrogen-containing compound that the ratio of the equivalents of isocyanate groups to the equivalents of active hydrogen groups, i.e., the foam index, is from about 0.9 to about 10 and in most cases from about 1 to about 4.
  • examples of polyisocyanates useful for making polyisocyanate-based foam comprise at least one of aromatic, aliphatic and cycloaliphatic polyisocyanates, among others.
  • Representative members of these compounds comprise diisocyanates such as meta- or paraphenylene diisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate, hexamethylene-1,6-diisocyanate, tetramethylene-1,4-diisocyanate, cyclohexane-1,4-diisocyanate, hexahydrotoluene diisocyanate (and isomers), napthylene-1,5-diisocyanate, 1-methylphenyl-2,4-phenyldiisocyanate, diphenylmethane-4,4-diisocyanate, diphenylmethane-2,4-
  • a crude polyisocyanate may also be used in the practice of this invention, such as the crude toluene diisocyanate obtained by the phosgenating a mixture comprising toluene diamines, or the crude diphenylmethane diisocyanate obtained by the phosgenating crude diphenylmethanediamine.
  • Specific examples of such compounds comprise methylene-bridged polyphenylpolyisocyanates, due to their ability to crosslink the polyurethane.
  • the polyisocyanate reactant can be a mixture of different polyisocyanates, and the active hydrogen-containing compound can be a mixture of different active-hydrogen-containing compounds.
  • the active hydrogen-containing compound and optionally other additives are mixed with the blowing agent to form a composition.
  • Such composition is typically known in the art as an isocyanate-reactive preblend, or B-side composition.
  • the B-side composition contains the active hydrogen-containing compound and preferably also contains the Z-1336mzz blowing agent.
  • the A-side composition preferably comprises the polyisocyanate.
  • the foam-forming composition comprising the A-side composition and the B-side composition can be prepared in any manner convenient to one skilled in this art, including simply weighing desired quantities of each component (ingredient) and, thereafter, combining them in an appropriate container at the temperatures and pressures desired.
  • additives comprise one or more members from the group consisting of catalysts, surfactants, flame retardants such as TCPP, preservatives, colorants, antioxidants, reinforcing agents, filler, and antistatic agents, among others well known in this art.
  • a surfactant can be employed to stabilize the foaming reaction mixture while curing.
  • Such surfactants normally comprise a liquid or solid organosilicone compound.
  • the surfactants are employed in amounts sufficient to stabilize the foaming reaction mixture against collapse and to prevent the formation of large, uneven cells.
  • about 0.1% to about 5% by weight of surfactant based on the total weight of the foamable composition i.e.total weight of all foaming ingredients (i.e. blowing agents + active hydrogen-containing compounds + polyisocyanates + additives,) are used.
  • about 1.5% to about 3% by weight of surfactant based on the total weight of all foaming ingredients are used.
  • One or more catalysts for the reaction of the active hydrogen-containing compounds, e.g. polyols, with the polyisocyanate may be also employed.
  • the selection of catalyst together with the reactants can favor formation of foamed polyisocyanurate instead of or mixed with foamed polyisocyanate in the practice of the process of the present invention.
  • any suitable urethane catalyst may be employed, specific catalyst comprise tertiary amine compounds and organometallic compounds. Exemplary such catalysts are disclosed, for example, in U.S. Patent No. 5,164,419 , which disclosure is incorporated herein by reference.
  • a catalyst for the trimerization of polyisocyanates such as an alkali metal alkoxide, alkali metal carboxylate, or quaternary amine compound, may also optionally be employed herein.
  • Such catalysts are used in an amount which measurably increases the rate of reaction of the polyisocyanate. Typical amounts of catalysts are about 0.1% to about 5% by weight based on the total weight of all foaming ingredients.
  • the active hydrogen-containing compound and said Z-1,1,1,4,4,4-hexafluoro-2-butene are combined into a composition, which is the B-side composition, prior to reacting the active-hydrogen-containing compound with the polyisocyanate.
  • this composition also comprises at least one of catalyst, surfactant, flame retardant.
  • this composition contains each of the catalyst, surfactant, and flame retardant.
  • the process of the present invention is not limited to the specifics disclosed above with respect to the polyisocyanate and active hydrogen-containing compound reactants and the additives present in the A-side or B-side compositions.
  • the relative amounts of polyisocyanate and active-hydrogen-containing compound reactants can be varied to obtain the foam desired, preferably a rigid foam.
  • Excess polyisocyanate reactant can provide a foamed reaction product of both polyurethane and polyisocyanurate.
  • the product of this reaction is foamed polyurethane or foamed polyisocyanurate, also depending on the identity of the polyisocyanate and active hydrogen-containing compound reactants and their relative amounts.
  • the polyurethane and polyisocyanurate reaction products (foamed) resulting from the process of the present invention are polymers.
  • these polymers are both produced by the reaction between polyol and polyisocyanate, they can be considered to be a mixture thereof.
  • the present invention is applicable to any foamable composition arising from the reaction of polyisocyanate with active hydrogen-containing compound.
  • the active hydrogen-containing compound, polyisocyanate and other components are contacted, thoroughly mixed, and permitted to expand and cure into a cellular polymer.
  • the mixing apparatus is not critical, and various conventional types of mixing head and spray apparatus are used.
  • conventional apparatus is meant apparatus, equipment, and procedures conventionally employed in the preparation of isocyanate-based foams in which conventional isocyanate-based foam blowing agents, such as fluorotrichloromethane (CCl 3 F, CFC-11), are employed.
  • conventional apparatus are discussed by: H. Boden et al. in chapter 4 of the Polyurethane Handbook, edited by G.
  • the temperature of polyisocyanate and active hydrogen-containing compound reactants fed to the mixing apparatus is preferably the same, which aids in viscosity matching of the reactants as an aid to complete mixing together.
  • This temperature is any of the foaming temperatures described above for practice of the present invention. At these high foaming temperatures, it is important that the mixing occurs quickly to accommodate the increased reaction rate accompanying these high temperatures. If the reactants are at a different temperature, it is preferred that the average of these different temperatures is at least one of the foaming temperatures described above for practice of the present invention. Viscosity matching can be accomplished by the reactants being at different temperatures.
  • the pressure of the apparatus to produce the spray of foaming reaction product can range from low pressure to high pressure.
  • Low pressure is considered to be 100 psi (0.69 MPa) or less, generally at least 50 psi (0.35 MPa).
  • High pressure is considered to be in the range of 1000 psi (6.9 MPa) to 2000 psi (13.8 MPa). These pressures are gauge pressure.
  • a preblend of certain raw materials is prepared prior to reacting the polyisocyanate and active hydrogen-containing components.
  • active hydrogen-containing compound blowing agent, surfactant(s), catalysts(s) and other foaming ingredients, except for polyisocyanates
  • B-side composition this blend (B-side composition) with the polyisocyanate.
  • all the foaming ingredients may be introduced individually to the mixing zone where the polyisocyanate and active hydrogen-containing compound are contacted. It is also possible to pre-react all or a portion of the active hydrogen-containing compound with the polyisocyanate to form a prepolymer.
  • composition and processes are applicable to the production of all kinds of polyurethane and/or polyisocyanurate foams, including, for example, integral skin, RIM and flexible foams, and in particular rigid closed-cell polymer foams useful in spray insulation, as pour-in-place appliance foams, or as rigid insulating board stock and laminates.
  • This process of the present invention also includes the making of foamed reaction products comprising closed-cell polyurethane or polyisocyanurate polymer.
  • foamed reaction products comprising closed-cell polyurethane or polyisocyanurate polymer.
  • the foam cells within the foamed reaction product are an average of at least 90% closed cells as determined in accordance with ASTM D 6226.
  • the process of the present invention produces high quality foamed structure, not only characterized by low density and high % closed cells as mentioned above, but also by density uniformity across the thickness of the foamed structure.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
  • “or” refers to an inclusive or and not to an exclusive or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
  • transitional phrase "consisting essentially of” is used to define a composition, method that includes materials, steps, features, components, or elements, in addition to those literally disclosed provided that these additional included materials, steps, features, components, or elements do not materially affect the basic and novel characteristic(s) of the claimed invention, especially the mode of action to achieve the desired result of any of the processes of the present invention.
  • the term 'consisting essentially of occupies a middle ground between “comprising" and 'consisting of.
  • the blowing agent is in the B-side (polyol) composition.
  • the foaming is carried out at temperatures of 110°F(43.3°C), 130°F(54.4°C) and 150°F(65.6°C).
  • the foaming results at these temperatures are reported in Table 1.
  • Thermal conductivity is the following units: Btu in/hr ⁇ ft 2° F (cal/cm ⁇ s ⁇ °C). Thermal conductivity is determined at 75°F(23.9°C).
  • the blowing agent is in the B-side (polyol) composition and the foaming is carried out at temperatures of 110°F(43.3°C), 130°F(54.4°C), and 150°F(65.6°C).
  • the foaming results at these temperatures are reported in Table 2.
  • Thermal conductivity is determined at 75°F(23.9°C). The units of thermal conductivity are the same as in Table 1.
  • the B-side composition used in both the Comparison Example and Example 1 is given in the following Table 3.
  • Table 3 - B-Side composition Ingredient Wt% Polyester polyol 31.25 Mannich polyol 32.10 Tris(chloropropyl)phosphate (TCPP) 14.00 Silicone surfactant 1.00 2-butoxy ethanol co-solvent 3.00
  • Glycerin 1.00 1,5-bis(dimethylamino)-3-oxapentane catalyst 0.70 2(-N,N,-dimethylaminoethyl-N-methylamino)ethanol catalyst 0.30 1,3-propanediamine,N-[3-(dimethylamino)propyl]-N,N',N'-trimethyl catalyst 2.60 Water 1.80 Z-1336mzz or HFC-245fa 12.25/10 Total 100.00
  • the polyester polyol has a hydroxyl number of 307 mg KOH/g, nominal functionality of 2.2, and dynamic viscosity of 5,500 cps (5.5 Pa ⁇ s) at 25°C.
  • the Mannich polyol has a hydroxyl number of 470 mg KOH/g, a nominal functionality of 4, and a dynamic viscosity of 10,000 cps (10.0 Pa ⁇ s) at 25°C.
  • the 12.25 wt% applies to the Z-1336mzz blowing agent and the 10 wt% applies to the HFC-245fa blowing agent. These different wt%s correspond to equal-molar concentrations of these blowing agents.
  • the amounts of the other ingredients in the composition can be adjusted to arrive at 100 wt% for the sum of all wt%s.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (7)

  1. Procédé comprenant le fait de faire réagir du polyisocyanate avec un composé contenant de l'hydrogène actif qui est le polyol en présence de Z-1,1,1,4,4,4-hexafluoro-2-butène à une température d'au moins 57,2°C (135°F) pour obtenir, comme résultat de cette étape, un produit réactionnel expansé.
  2. Procédé selon la revendication 1, ladite température étant de 57,2°C (135°F) à 65,6°C (150°F).
  3. Procédé selon la revendication 1, ladite température étant de 60,0°C (140°F) à 65,6°C (150°F).
  4. Procédé selon la revendication 1, ledit produit réactionnel étant le polyuréthane polyisocyanurate, ou un mélange de ces polymères.
  5. Procédé selon la revendication 1, ledit composé contenant de l'hydrogène actif et ledit Z-1,1,1,4,4,4-hexafluoro-2-butène étant combinés en une composition avant ladite réaction avec ledit polyisocyanate.
  6. Procédé selon la revendication 5, ladite composition comprenant également au moins l'un d'un catalyseur, tensioactif, agent ignifuge.
  7. Procédé selon la revendication 6, ladite composition contenant chacun dudit catalyseur, tensioactif, et agent ignifuge.
EP17702249.8A 2016-01-22 2017-01-18 Utilisation du z-hfo-1,1,1,4,4,4-hexafluoro-2-butène dans des applications d'expansion à haute température Active EP3405515B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201662281948P 2016-01-22 2016-01-22
PCT/US2017/013883 WO2017127402A1 (fr) 2016-01-22 2017-01-18 Utilisation du z-hfo-1,1,1,4,4,4-hexafluoro-2-butène dans des applications d'expansion à haute température

Publications (2)

Publication Number Publication Date
EP3405515A1 EP3405515A1 (fr) 2018-11-28
EP3405515B1 true EP3405515B1 (fr) 2020-04-29

Family

ID=57915151

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17702249.8A Active EP3405515B1 (fr) 2016-01-22 2017-01-18 Utilisation du z-hfo-1,1,1,4,4,4-hexafluoro-2-butène dans des applications d'expansion à haute température

Country Status (8)

Country Link
US (1) US10155856B2 (fr)
EP (1) EP3405515B1 (fr)
JP (2) JP2019504912A (fr)
CN (1) CN108473711B (fr)
CA (1) CA3010214C (fr)
ES (1) ES2797960T3 (fr)
MX (1) MX2018008828A (fr)
WO (1) WO2017127402A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019067939A1 (fr) * 2017-09-29 2019-04-04 The Chemours Company Fc, Llc Composition d'agent gonflant pour la préparation d'une mousse
CN109294218A (zh) * 2018-09-28 2019-02-01 上海东大聚氨酯有限公司 组合聚醚、聚氨酯泡沫原料组合物、源自其的聚氨酯泡沫及其制备方法和应用
US11732081B2 (en) * 2021-06-08 2023-08-22 Covestro Llc HCFO-containing isocyanate-reactive compositions, related foam-forming compositions and flame retardant PUR-PIR foams

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4394491A (en) 1980-10-08 1983-07-19 The Dow Chemical Company Addition polymerizable adduct of a polymeric monoahl and an unsaturated isocyanate
US5164419A (en) 1991-05-20 1992-11-17 E. I. Du Pont De Nemours And Company Blowing agent and process for preparing polyurethane foam
JPH05179043A (ja) * 1991-11-18 1993-07-20 Daikin Ind Ltd フルオロブテンからなる発泡剤およびプラスチック発泡体の製造方法
MY151990A (en) * 2005-11-01 2014-07-31 Du Pont Solvent compositions comprising unsaturated fluorinated hydrocarbons
CA2688087C (fr) * 2007-07-20 2014-09-09 E. I. Du Pont De Nemours And Company Compositions et utilisation d'une composition moussante de cis-1,1,1,4,4,4-hexafluoro-2-butene dans la preparation de mousses a base de polyisocyanate
US20110269860A1 (en) * 2010-04-28 2011-11-03 E.I. Du Pont De Nemours And Company Foam expansion agent compositions containing hydrohaloolefin butene and water and their uses in the preparation of polyurethane and polyisocyanurate polymer foams
US9145480B2 (en) * 2010-10-28 2015-09-29 Honeywell International Inc. Mixtures containing 1,1,1,3,3,3-hexafluorobutene and 1-chloro-3,3,3-trifluoropropene
WO2012105657A1 (fr) * 2011-02-02 2012-08-09 旭硝子株式会社 Procédé pour la production de résine synthétique expansée dure
CA2789150A1 (fr) * 2011-09-06 2013-03-06 Basf Se Mousse de polyurethane et composition de resine
EP2785777A1 (fr) 2011-12-02 2014-10-08 E. I. Du Pont de Nemours and Company Compositions d'agent d'expansion de mousse contenant du z-1,1,1,4,4,4-hexafluoro-2-butène et leurs utilisations dans la préparation de mousses de polymère de polyuréthane et de polyisocyanurate
WO2013082963A1 (fr) * 2011-12-09 2013-06-13 Honeywell International Inc. Mousses et articles fabriqués à partir de mousses contenant des agents gonflants hcfo ou hfo
CA2898036C (fr) 2013-01-15 2021-01-26 Basf Se Mousse rigide
WO2015099086A1 (fr) 2013-12-27 2015-07-02 旭化成建材株式会社 Mousse de résine phénolique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
US10155856B2 (en) 2018-12-18
JP2022179581A (ja) 2022-12-02
CA3010214C (fr) 2023-09-19
US20170210870A1 (en) 2017-07-27
EP3405515A1 (fr) 2018-11-28
MX2018008828A (es) 2018-09-17
CA3010214A1 (fr) 2017-07-27
JP7482961B2 (ja) 2024-05-14
WO2017127402A1 (fr) 2017-07-27
ES2797960T3 (es) 2020-12-04
CN108473711A (zh) 2018-08-31
CN108473711B (zh) 2021-08-06
JP2019504912A (ja) 2019-02-21
KR20180104297A (ko) 2018-09-20

Similar Documents

Publication Publication Date Title
EP2215154B1 (fr) Compositions et utilisation d'une composition moussante à base de cis-1,1,1,4,4,4-hexafluoro-2-butène pour la préparation de mousses à base de polyisocyanate
AU2018236730B2 (en) Foam expansion agent compositions containing hydrohaloolefin and water and their uses in the preparation of polyurethane and polyisocyanurate polymer foams
EP2567993B1 (fr) Compositions moussantes contenant un mélange azéotropique ou de type azéotropique contenant du cis-1,1,1,4,4,4-hexafluoro-2-butène et du cyclopentane et leurs applications dans la préparation de mousses à base de polyisocyanate
US20100210747A1 (en) Compositions and use of trans-1,1,1,4,4,4-hexafluoro-2-butene foam-forming composition in the preparation of polyisocyanate-based foams
JP7482961B2 (ja) 高温発泡用途におけるz-hfo-1,1,1,4,4,4-ヘキサフルオロ-2-ブテンの使用
EP3405516B1 (fr) Moussage d'un produit de réaction d'un polyisocyanate et d'un composé contenant de l'hydrogène actif
US20110124758A1 (en) Foam-forming compositions containing mixtures of 2-chloro-3,3,3-trifluoropropene and hydrocarbon and their uses in the preparation of polyisocyanate-based foams
EP2393862B1 (fr) Compositions formant une mousse contenant des mélanges de cis-1,1,1,4,4,4-hexafluoro-2-butène et de 1,1,1,3,3-pentafluoropropane et leurs utilisations dans la préparation de mousses à base de polyisocyanate
AU2018201150A1 (en) Foam-forming compositions containing azeotropic or azeotrope-like mixtures containing z-1,1,1,4,4,4-hexafluoro-2-butene and their uses in the preparation of polyisocyanate-based foams
CN109689753B (zh) 具有z-1,1,1,4,4,4-六氟丁烯的泡沫
WO2006044604A9 (fr) Mousses rigides aux bonnes proprietes isolantes et leur procede de production
KR102716255B1 (ko) 고온 발포 응용에서의 z-hfo-1,1,1,4,4,4-헥사플루오로-2-부텐의 사용
EP0914369B1 (fr) Utilisation de melanges d'agents gonflants dans la preparation de mousses a base de polyisocyanate
KR102716246B1 (ko) 폴리아이소시아네이트/활성 수소-함유 화합물 반응 생성물의 발포

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20180803

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

DAV Request for validation of the european patent (deleted)
DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20190520

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20191216

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1263206

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200515

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602017015639

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200730

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200831

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200729

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200829

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1263206

Country of ref document: AT

Kind code of ref document: T

Effective date: 20200429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200729

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2797960

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20201204

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602017015639

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20210201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210118

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210131

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210131

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210118

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230516

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20170118

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20231219

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20231219

Year of fee payment: 8

Ref country code: FR

Payment date: 20231219

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20231219

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20240202

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20231219

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20240102

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20200429